Corrosion Science 209 (2022) 110731

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Hot corrosion behavior of APS YSZ coatings treated by laser micro glazing
(LMG) under molten salts (V2O5 +Na2SO4)
Kun Huo a, Fengze Dai a, *, Wei Qian a, Yunxia Ye a, Jie Cai a, Yinqun Hua a, Xiaofeng Zhang b
a
School of Mechanical Engineering, Jiangsu University, Zhenjiang 212013, PR China
b
Institute of New Materials, Guangdong Academy of Science, Guangzhou 510650, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, yttria-stabilized zirconia (YSZ) coatings prepared by atmospheric plasma spraying (APS) were
Yttria-stabilized zirconia coatings glazed by a nanosecond pulsed laser (laser micro glazing, LMG). The hot corrosion mechanism of as-sprayed,
Atmospheric plasma spraying ground, and LMGed YSZ coatings was investigated at a temperature of 1100 ºC in V2O5 and Na2SO4 molten
Laser micro glazing
salts for 20 h. The results show that a dense LMGed layer with narrow network of segmented microcracks (sub-
Molten salts
Hot corrosion
micron level) was formed after the LMG process. Compared to the single-time LMG, pores can be effectively
eliminated after six-times laser irradiation. The hot corrosion behavior of YSZ coatings exposed to molten V2O5
+Na2SO4 demonstrates that pores in the single-time LMGed layer seriously affect its hot corrosion resistance.
After multiple LMG, the volume fraction of the m-ZrO2 decreases from 53% to 27% with the disappearance of
pores. The quantity of the corrosion products YVO4 was greatly reduced and the depth of the damaged area
diminished from 37.073 µm to 20.918 µm, which shows a significant improvement in molten salts corrosion
resistance.

1. Introduction
Thermal barrier coatings (TBCs) increase the working temperatures
of turbine blades by providing thermal insulation, which has been
widely applied in aero gas turbines to improve thermal efficiency,
durability, and thrust loading [1]. The typical TBCs system is composed
of an insulating ceramic coating on the upper layer, followed by a
metallic bond coating (BC) with a thermally grown oxide (TGO) in the
middle and a superalloy substrate at the bottom [2,3]. Considering the
excellent physical properties of TBCs such as small thermal conductivity,
large coefficient of thermal expansion, low density, and high melting
point, 6–8 wt% yttria-stabilized zirconia (YSZ) has been widely utilized
as a top ceramic coating [4,5]. Usually, YSZ coatings are fabricated by
atmospheric plasma spraying (APS), electron beam physical vapor
deposition (EB-PVD), and plasma spray-physical vapor deposition
(PS-PVD) technologies [6–8]. APS has the best thermal insulation effect,
the lowest cost, and the highest deposition efficiency, which has
extensive application in chamber parts and vanes [9–11].
YSZ is susceptible to corrosion at high temperatures when it is
exposed to low-quality industrial fuel containing sulphur (S), sodium
(Na), and vanadium (V) impurities [12–14]. The defects such as high
surface roughness, pores, and inter-splat and intra-splat cracks in APS
YSZ coatings can accelerate the hot corrosion process [15]. Many works
have been carried out to slow down the hot corrosion of V2O5 +Na2SO4.
Zhang et al. [16], Chen et al. [17], and Afrasiabi et al. [17,18]deposited
an Al2O3 layer on the YSZ coatings. The dense and chemically inert
Al2O3 deposition can effectively block the penetration of molten salts at
high temperatures, which improves corrosion resistance. Roche et al.
[19], and Park et al. [20] investigated the effect of the addition of rare
earth ceria (Ce) in the YSZ coating. The authors reported that tetragonal
zirconia (t′ -ZrO2) in YSZ is more stable, and the phase transformation is
less prone to be induced in the molten salts with the presence of strong
acidic CeO2. Habibi et al. [21] mixed Gd2Zr2O7 into YSZ during the APS
process. In the hot corrosion test, Gd reacts with V in the molten salts to
form GdVO4, reducing the corrosion products and improving the
corrosion resistance. Nevertheless, by changing the components of
ceramic coatings, their mechanical properties were weakened, espe­
cially the toughness and cyclic life [22,23].
Laser processing is a promising alternative approach for enhancing
the hot corrosion resistance of YSZ coatings. Batista et al. [24], Yi et al.
[25], and Varghese et al. [26] applied a continuous wave laser beam to
remelt the YSZ surface, and a glazed layer was attained. Laser glazing

* Corresponding author.
E-mail address: dfz@ujs.edu.cn (F. Dai).

https://doi.org/10.1016/j.corsci.2022.110731
Received 4 July 2022; Received in revised form 5 October 2022; Accepted 6 October 2022
Available online 12 October 2022
0010-938X/© 2022 Elsevier Ltd. All rights reserved.
K. Huo et al. Corrosion Science 209 (2022) 110731

greatly reduces the surface roughness and forms a dense columnar layer
during rapid solidification, which can effectively improve the hot
corrosion performance of YSZ. However, due to high local energy and
uneven cooling rate, wide networks of segmented cracks (more than 20
µm) are formed [27]. These wide cracks provide channels for molten
salts penetration, which makes the corrosion resistance of the remelted
layer insignificantly improved. To effectively narrow the crack width,
Guo et al. [28] used a millisecond pulsed laser. The crack width of the
remelted layer is reduced to 5–10 µm by reducing the heat-affected zone
and optimizing the processing parameters, thereby promoting better
corrosion resistance in molten salts. Furthermore, Fan et al. [27]
induced ultrasonic assistance in the millisecond pulsed laser glazing
process. The enhanced mass and heat transfer reduces local high thermal
stress in the remelted layer, resulting in denser and finer cracks (<3 µm)
on the YSZ coatings. Fan et al. [29] also explored the application of
femtosecond pulsed laser to remelt YSZ coatings. The effect of the
remelting produced small surface roughness, pore healing, and
nano-particles, which enhances the corrosion resistance of YSZ coatings.
However, with ultrashort pulse duration and small thermal effect, the
columnar glazed layer was not generated. In general, wider cracks
weaken the hot corrosion resistance, although the remelt layer can resist
the molten salt corrosion. Therefore, controlling the width of the
microcrack is the key to improving the resistance of laser remelted
layers.
To overcome the drawbacks of continuous wave and ultrashort
pulsed laser polishing, a nanosecond pulsed laser was used to treat the
YSZ coatings in this paper. The aim is to achieve narrow microcracks and
columnar glazed layers. The hot corrosion mechanism of APS YSZ in
molten V2O5 +Na2SO4 was systematically studied.
2. Experimental
2.1. Materials and coating preparation
The polycrystalline alumina with the dimension of 10 mm × 10
mm× 5 mm (LU YANG, China) was chosen as the substrate, which can be
tolerated at higher temperatures than metals [30]. The 8 wt%
yttria-stabilized zirconia (YSZ) powder (Sulzer Metco, Switzerland) was
deposited on the substrate using the air plasma spraying (APS, Sulzer
Metco, Switzerland) as a top ceramic coating. The APS process param­
eters are shown in Table 1.
2.2. Laser micro glazing (LMG)
The as-sprayed YSZ coatings were ground with the 1000–2000 grit
SiC papers to improve the surface quality before LMG. Then, the ground
coatings were placed in absolute ethanol, cleaned with an ultrasonic
cleaner for 30 min, and dried at 100 ºC for 2 h step by step. The coatings
were irradiated by a 100 W nanosecond pulsed laser (YDFLP-60-M7-M-
R, JPT, China) with a wavelength of 1064 nm, as seen in Fig. 1. The
optimized parameters used to treat the surface morphology (the width of
microcracks) are listed in Table 2. It was observed that the surface
morphologies of YSZ coatings were different from the single and mul­
tiple times LMG. The influence of the morphologies on the corrosion
resistance of V2O5 +Na2SO4 was examined by fabricating four kinds of
Table 1
Air plasma spraying parameters for YSZ coatings.
Parameters Values
Current (A) 580
Primary gas, Ar (L/min) 60
Secondary gas, H2 (L/min) 11
Carrier gas, Ar (L/min) 3 B
Feedstock giving rate (g/min) 21
Spray distance (mm) 120
Fig. 1. Schematic diagram of LMG YSZ coatings.
Table 2
LMG parameters for YSZ coatings.
Power Scanning Overlap Spot Frequency Pulse
(W) speed (mm/ rate (%) diameter (kHz) duration
s) (μm) (ns)
10 300 75 20 100 30
YSZ coatings, as seen in Table 3.
2.3. Hot corrosion tests
The molten salts contain a mixture of 55 wt% NaSO4, and 45 wt%
V2O5, which was evenly applied on the surface of the coating at 20 mg/
cm2. The molten salts were applied 3 mm away from the edge of samples
to avoid the edge effect; to prevent the molten salts from infiltrating
samples inwardly from the edge. The applied coating was placed in a dry
box (DHG101–1A, China) for 3 h to remove moisture and increase the
adhesion of molten salts. Finally, the coatings were heated in the box-
type electric lab furnace (SXL-1400, SIOMM, China) at 1100 ºC for
20 h. After cooling to room temperature in the furnace, the samples were
cleaned in absolute ethanol using an ultrasonic cleaner for 15 s to
eliminate excess corrosion mixtures and dust.
2.4. Characterization
In order to observe the LMGed layers after the LMG process, frac­
tured cross-section morphologies were used. A shallow groove (non-
penetration) was sawed out from the bottom on the alumina substrate
along the direction of YSZ growth. The alumina substrate with the 8YSZ
coating is then disconnected. The polished cross-section SEM samples
for backscattered electron (BSE) images were prepared by first embed­
ding the molten salt etched samples in epoxy resin. They were then cut
in the same direction (penetration). The cut samples were polished with
SiC abrasive paper of progressively finer grain size. The surface and
cross-section of YSZ coatings were observed by field emission scanning
electron microscopy (FESEM, JSM-7001 F, JEOL, Japan) before and
after the hot corrosion tests. The surface roughness of coatings was
measured via laser confocal microscopy (KEYENCE, VK-X250k, Japan).
X-ray diffraction (XRD; D8 ADVANCE, Bruker, Germany) was used to
determine the phase compositions of coatings. The XRD patterns were at
the 2θ range of 20º to 90º with a scanning speed of 2◦ /min. The
Table 3
Experimental conditions of YSZ coatings.
Coating YSZ coating
A As-sprayed
Ground
C Single-time LMGed
D Six-times LMGed

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K. Huo et al.
proportion of m-ZrO2 in coatings was calculated by XRD patterns at the
2θ range of 27◦ − 33◦ with a scanning speed of 0.2◦ /min.
3. Results and discussion
3.1. Characterization of coatings before hot corrosion tests
3.1.1. Top surface morphology
From Fig. 2(a), it can be seen that there are pores, unmelted powder,
and microcracks existing in coating A. During the APS process, the
molten YSZ powder quickly hits on the surface of the substrate, flat­
tening into the splats. The gaps between the horizontal splats form pores
in the stacking process, with the feedstock giving of YSZ powder [31,
32]. At the same time, under the action of thermal stress, microcracks
are also formed during the splats cooling process. Typical laminar
structures are found in pores, accompanied by through-type cracks. In
Fig. 2(b), mechanical grinding can remove most of the unmelted powder
on the surface of YSZ. However, spallation, pores, and microcracks
cannot be removed completely. As mentioned before, pores are the
characteristics of the APS process, which exist in the entire YSZ coatings,
reducing the thermal conductivity [25].
After the irradiation by the laser energy, the ground YSZ surface
melts, and most of the pores are reduced in size, as shown in Fig. 2(c).
The smooth inner wall of the pore does not show a layered structure,
proving that pores were remelted. The network of segmented micro­
cracks appears on the YSZ coating surface, with the release of quenching
stresses in the uneven and rapid cooling process. Unlike the continuous
and millisecond pulsed laser that produces wide (several micrometers)
microcracks, the nanosecond laser has shorter pulse width and action
time, which induces a smaller heat-affected zone and thermal stress. The
reduced heat reunion in the molten pool is prone to form dense and
narrow microcracks (sub-micron level, <1 µm), which is not conducive
to the penetration of molten salts [27]. During the glazing process, the
plasma induced by laser energy explodes in the molten pool. Under its
impact, the YSZ splashes and solidifies to form irregular spatters along
the scanning direction [33]. With the increase in LMG process times, the
spatters are more evident, and the pores disappear gradually (Fig. 2d).
Fig. 2. Surface morphologies of coatings before the hot corrosion, (a) as-sprayed, (b) ground, (c) single-time LMGed, (d) six-times LMGed.
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Corrosion Science 209 (2022) 110731
Here, two factors cause these phenomena. Firstly, multiple LMG melts
the edges of pores, which leads to the liquid YSZ gradually flowing into
pores, reducing their depth. Secondly, the enhancement of spatters in­
creases the probability of covering the top surface of pores and sealing
the pores.
3.1.2. Cross-section morphology
The cross-section morphologies of four YSZ coatings are shown in
Fig. 3. Fig. 3(a) shows that the inter-, intra-splat cracks and pores in
coating A are obvious. These features become the penetration channel of
molten salts during the hot corrosion process, destroying the YSZ and
reducing its service life [27]. The uneven splat thickness and overlap
cause the YSZ to form a curved laminar structure during the
layer-by-layer stacking process (Fig. 3b). The columnar grains with a
high aspect ratio are formed in every individual splat. During the so­
lidification process, the upper part of each splat has a lower temperature
than the bottom part, causing the grains to grow directionally along the
cross-section [34]. In coating B, the unmelted powder on the YSZ surface
is removed, exposing the underlying inter splat cracks and pores, which
increase the intrusion channels of molten salts during the corrosion
process (Fig. 3c,d) [35].
Fig. 3(e,f) shows that the surface of coating C is glazed and solidified
by laser irradiation. Due to the relatively low local energy of the
nanosecond laser, the high aspect ratio of the grain is reduced, forming
wider and denser columnar grains with ~3.164 µm in length. This can
greatly eliminate the impact on thermal conductivity of LMGed coatings
(2 W/m K for the LMGed layer and 1.5 W/m K for the splat). The LMGed
layer is well bonded with the underlying splats and no obvious trans­
verse cracks were found. This indicates that the LMGed layer forms small
shear stresses with the underside during the solidification process and is
less prone to spalling [36]. The pores between each spalt become bub­
bles and rise during the glazing process. However, due to the extremely
short solidification time, some of them remain in the grains. Meanwhile,
the shrinkage and thermal stress of YSZ form longitudinal microcracks
throughout the remelted layer. In Fig. 3(g,h), coating D indicates that
multiple LMG processes cannot increase the depth of the remelted layer,
change the size of columnar crystals, and eliminate microcracks.
K. Huo et al.
Fig. 3. Fractured cross-section morphologies of coatings before the hot corrosion, (a,b) as-sprayed, (c) ground, (d) single-time LMGed, (e) six-times LMGed.
However, it is more beneficial to make the bubbles completely disappear
in the columnar grains, which is consistent with the elimination of pores
on surface (Fig. 2d).
3.1.3. Surface roughness
The 3D topographies of the four coatings are shown in Fig. 4. The
surface roughness (Ra) of 6.704±0.245 µm for coating A is extremely
high, due to the curved laminar structure and unmelted powder
(Fig. 4a). In Fig. 4(b), after mechanical grinding, most of the unmelted
powder is removed. The Ra for coating B decreases to 1.260±0.457 µm
owing to the presence of pores. As shown in Fig. 4(c,d), even though the
pores are smaller or disappear after the laser polishing, the spatters
induced by laser irradiation still cause the Ra of 2.339±0.598 and
2.890±0.895 µm in the case of coating C and D, respectively. This is
consistent with the results reported by Fan et al. [29].
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Corrosion Science 209 (2022) 110731
3.1.4. Phase composition
Fig. 5 shows the XRD patterns of 4 coatings from 20◦ − 90◦ before the
hot corrosion. The result indicates that t′ -ZrO2 is the main component of
all YSZ coatings and there is no phase transformation after LMG. This
kind of non-equilibrium phase has a low thermal conductivity and does
not undergo phase change during the cooling process. Simultaneously,
the quick cooling rate of LMG (103-104 K/s) avoids the poor phase
transformation of the nonequality t′ phase into the monoclinic phase (m-
ZrO2) [37].
3.2. Hot corrosion behavior
After a 20 h hot corrosion test at 1100 ºC with molten V2O5
+Na2SO4, the micrographs of YSZ surfaces are shown in Fig. 6. The rod-
shaped crystals are corrosion products distributed in piles on coating A,
as seen in Fig. 6(a). The high surface roughness (Ra 6.704 µm) due to the
curved laminar structure, unmelted powder, and pores in coating A
K. Huo et al.
Fig. 4. Surface roughness of coatings before the hot corrosion, (a) as-sprayed, (b) ground, (c) single-time LMGed, and (d) Six-times LMGed.
Fig. 5. XRD patterns of coatings (a) as-sprayed, (b) ground, (c) single-time
LMGed, and (d) six-times LMGed before the hot corrosion tests.
increases the specific area between the molten salts and coatings
significantly. At higher magnification, it can be found that most of the
rod-shaped crystals are distributed on the top of pores. In Fig. 6(b), after
the mechanical grinding, the distribution of rod-shaped crystals is more
uniform. The amount of crystals is slightly reduced, and some are still
found in pores. The single-time LMG seems to have weakened the
corrosion resistance of coating C, as shown in Fig. 6(c). The YSZ coating
suffers severe corrosion attacks, and the rod-shaped corrosion products
cover almost the entire surface. The size and aspect ratio of corrosion
products significantly increased by 2–3 times than before. In coating D,
the scanning paths are more visible, and the corrosion products are
reduced in amount greatly. It indicates that corrosion resistance has
been significantly improved by six-times LMG (Fig. 6d).
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Corrosion Science 209 (2022) 110731
The regions around corrosion products in Fig. 6 exhibit two different
shapes of the product after the hot corrosion test, as seen in Fig. 7. Blocks
are densely packed together compared to small particles that are loosely
piled up together. The proportion of small particles in regions is pro­
portional to the content of the corrosion products. There are slightly
more blocks in coating B than in coating A (Fig. 7a,b). A completely
different phenomenon is observed in coating C and D due to the different
corrosion resistance. Small particles fill the entire coating C, and large
blocks are the majority of coating D (Fig. 7c,d). The presence of blocks
can effectively inhibit the further penetration of molten salts in the hot
corrosion tests.
The chemical compositions of various phases in four coatings are
shown in Fig. 6(e) and 7 (e). It is observed that rod-shaped corrosion
products mainly consist of yttrium, vanadium, and oxygen, with a small
amount of zirconium. Blocks and small particles distributed around the
corrosion products mainly consist of oxygen and zirconium, with and
without yttrium. Based on the XRD analysis in Fig. 8, it can be inferred
that the corrosion products are mainly YVO4, the blocks are t′ -ZrO2
grains riching Y and small particles are m-ZrO2 grains leaching Y.
In Fig. 8, the XRD patterns show that the four types of YSZ coatings
were dominated by YVO4, t′ -ZrO2, and m-ZrO2 after the hot corrosion
tests. The intensity of rod-shaped YVO4 reflects the corrosion resistance
and is consistent with the trend in Fig. 6. Mechanical grinding can
improve corrosion resistance to a certain extent relative to the as-
sprayed YSZ coating. Nevertheless, the corrosion resistance of YSZ
coatings is completely different after single and six-times LMG, which is
poor in coating C and excellent in coating D.
Besides, the volume fraction of m-ZrO2 (27◦ − 33◦ ) in the YSZ coat­
ings after the hot corrosion test can also quantitatively reflects the
corrosion resistance [38] (Fig. 9). It can be calculated by the following
equation [39]:
m% =
Im (111) + Im (111)
× 100% (1)
Im (111) + Im (111) + It (111)
where I is the peak diffraction intensity of ZrO2. The volume fraction of
K. Huo et al. Corrosion Science 209 (2022) 110731

Fig. 6. FESEM micrographs of coatings after the hot corrosion, (a) as-sprayed, (b) ground, (c) single-time LMGed, (d) six-times LMGed, (e) composition analysis of
the surface.

Fig. 7. FESEM micrographs of (a) region in Fig. 6(a), (b) region in Fig. 6(b),(c) region in Fig. 6(c), (d) region in Fig. 6(d), (e) composition analysis of surface.

m-ZrO2 in coating A, B, C, and D are 53±5.345%, 40±6.887%,
86±7.574%, and 27±4.654%, respectively. The m phase in coating D is
the least and compared with coating A, the phase transformation is
reduced by nearly half.
Further examination of the corrosion resistance of the coatings was
done by observing the cross-sectional morphologies using FESEM, as
shown in Fig. 10. Mineralization of YSZ exists in coating A, which in­
dicates the occurrence of phase transformation from t′ to m phase. The
original columnar grains in splats turn into small particles, reducing the
bonding between the splats. Thus, the spallation occurs at the top of
coating A Fig. 10(a,b). The back scattered-electron (BSE) morphologies
are shown in Fig. 10 (c,d). The YVO4 exists in the whole coating due to
the penetration of V. Nevertheless, the erosion is more pronounced and
severe in the upper layer. The YVO4 is densely distributed in the upper
layer which is defined as damaged areas. The wavy YVO4 only exists in
the inter-splat cracks due to the delamination of splats (the broken line is
the decomposition line). The depth of damage area in coating A is
approximately 37.073 µm.

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K. Huo et al.
Fig. 8. XRD patterns of YSZ coatings after hot corrosion tests,as-sprayed, (b) ground, (c) single-time LMGed, (d) six-times LMGed.
In coating B, the mechanical grinding does not decrease the degree of
mineralization after the hot corrosion test, although the surface rough­
ness is significantly reduced (Fig. 11a). After mechanical polishing in the
cross-section, the small particle-shaped m-ZrO2 is exposed, as seen in
Fig. 11 (b). The depth of the damaged area is similar to that of coating A
around 33.231 µm, with YVO4 evenly distributed in it (Fig. 11c,d).
These phenomena suggest that there is no relationship between Ra and
molten salt penetration.
After single-time LMG, the upper layer of coating C suffers from se­
vere mineralization and spallation, despite the presence of the LMGed
layer (Fig. 12a). In Fig. 12(b), the fractured cross-section morphologies
reveal that the top is essentially full of small particle-shaped m-ZrO2,
visibly contrasting with the lamellar structure below. The YVO4 is
interspersed between the particles, as the corrosion product of Y
leaching. The depth of the damaged area is 36.224 µm, which is similar
to that of coating A and B. This indicates that the single-time LMG
process does not provide resistance to molten salt either due to the ex­
istence of pores (Fig. 12c,d).
The cross-section morphologies of six-times LMGed coatings are
shown in Fig. 13. Compared to the other 3 coatings, the mineralization
degree is the least in coating D, suggesting the least phase trans­
formation occurrence (Fig. 13a,b). As seen in Fig. 13 (c,d), the depth of
the damaged area in coating D is also suppressed by half to only about
20.918 µm. The density and content of corrosion products are also
reduced, indicating the penetration of molten salts was significantly
hindered by the dense and integrated LMGed layer.
To quantify the corrosion resistance, the EDS mapping results of
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Corrosion Science 209 (2022) 110731
Fig. 10 (c), Fig. 11 (c), Fig. 12 (c) and Fig. 13 (c) are shown in Fig. 14
(1− 3). It can be seen that in coatings A-C, the V element penetrates and
spreads throughout the coatings, mostly concentrated in the damaged
areas. There, the leached Y forms YVO4 with V, resulting in the aggre­
gation. The penetration of V in coating C increases slightly more than in
coating A and B, from 2.83 wt% and 2.84–3.57 wt%, respectively. In
coating D, the aggregation of V in the whole coating is not significant
due to the apparent reduction of V to 1.18 wt%, a 58.45% reduction
compared to coating A (Fig. 12c4).
3.3. Hot corrosion mechanism
Hot corrosion is an extremely complex process with the penetration
of molten salts, which also entails the leaching of Y and the inward
diffusion of V [40]. The corrosion mechanism of the four coatings is the
same, but there exist different corrosion resistance and are characterized
by the following processes:
Firstly, when the molten mixture of Na2SO4 and V2O5 is exposed to
1000 ◦ C, the Na2SO4 decomposes to form Na2O and SO3, which further
react with V2O5 to form NaVO3 [41]:
Na2 SO4 (I)→Na2 O(I) + SO3 (g) (2)
V2 O5 (I) + Na2 O(I)→2NaVO3 (I) (3)
Then, the liquid Na2SO4, V2O5, and NaVO3 penetrate more easily into
the defective coating surfaces, further aggravating the hot corrosion.
The reactions of NaVO3, V2O5, and Y2O3 are shown below [42]:
K. Huo et al. Corrosion Science 209 (2022) 110731

Fig. 9. XRD patterns of coatings in 2 Theta range 27◦ − 33◦ after hot corrosion tests, (a) as-sprayed, (b) grinding, (c) single-time LMGed, (d) six-times LMGed.

Fig. 10. Cross-section morphologies of the as-sprayed coatings after the hot corrosion test.

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K. Huo et al. Corrosion Science 209 (2022) 110731

Fig. 11. Cross-section morphologies of the ground coatings after the hot corrosion test.

Fig. 12. Cross-section morphologies of single-time LMGed coatings after the hot corrosion test.

ZrO2 • Y2 O3 (s) + 2NaVO3 (I)→m-ZrO2 (s) + 2YVO4 (s) + Na2 O(I)
Y2 O3 (s) + V2 O5 (I)→2YVO4 (s)
With the leaching of Y, this kind of martensitic-type of phase trans­
formation will result in 3–5% volume expansion, causing stress,
microcracks, and spalling [43]. So in Fig. 7, increased phase trans­
formation forms smaller particle-shaped m-ZrO2, which is confirmed by
the XRD patterns in Fig. 10. The Na and S contents in the coating were
reduced due to evaporation in the form of Na2O and SO3 (Table 4), this is
similar to previous studies in the literature [44].
(4) Fig. 13 shows a schematic diagram that illustrates the molten salt
penetration in the pre-corrosion period. According to the effective
(5) permeation coefficient k described by Carman–Kozeny model [45]:
r2 φ2
k= (6)
8τ(1 − φ)2
where τ is the medium tortuosity, φ is the overall porosity of the me­
dium, and r is the radius of the pores. The τ increases in a parabolic
pattern as the φ decreases [46]. The inter-, intra splat cracks, and pores
supply the infiltration channels to the next splat, which accelerate the

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K. Huo et al. Corrosion Science 209 (2022) 110731

Fig. 13. Cross-section morphologies of six-times LMGed coatings after the hot corrosion test.

Fig. 14. Elemental mapping images of cross-section in (a) as-sprayed, (b)ground, (c) single-time LMGed, (d) six-times LMGed coatings in the region of Fig. 10(c),
Fig. 11(c), Fig. 12(c), Fig. 13 (c), respectively.

10
K. Huo et al.
hot corrosion (Fig. 10c). Though the reduction of coating B surface
roughness has a positive effect on the corrosion resistance, more open
pores and inter-splat cracks are exposed after the mechanical grinding.
The molten salts penetrate easily, which results in a slight reduction of
YVO4 on the surface (Fig. 6b), but no reduction in corrosion depth
(Fig. 11c). The corrosion resistance is seriously weakened by single-time
LMG in coating C. Many pores were locally concentrated with molten
salts, making them more susceptible to corrosion than flat regions. The
distance required for the molten salt to infiltrate the remelted layer is
much shorter than the flat regions (Fig. 14c). This makes it difficult for
the remelted layer to play a barrier role in blocking molten salts. The
dense remelted layer without pores in coating D can effectively decrease
the permeation coefficient of molten salts (Fig. 14d). The narrow
microcracks (sub-micron level, <1 µm) are also self-healing during
thermal and volume expansion (t′ →m transformation), which has been
proven to be detrimental to the penetration of molten salt by Fan et al.
[47]. In addition, the melting of the unmelt powder and the mass and
heat transfer result in a more uniform distribution of Y2O3 in the LMGed
layer [48]. Compared to other coatings, molten salt is really hard to find
breaches in coating D.
The reaction of YSZ and molten salts depends not only on the
penetration of molten salts but also on the active leaching of Y. The
formula (4) can be further divided into:
NaV O3 (I)
ZrO2 • Y2 O3 (s) ̅̅̅̅→ m-ZrO2 (s) + Y2 O3 (s) (7)
Y2 O3 (s) + 2NaVO3 (I)→2YVO4 (s) + Na2 O(g) (8)
In Fig. 15, the schematic diagram of Y leaching and V diffusion are
clearly described. In the first step, the Y at the interface between the
molten salts and coatings reacts with NaVO3 and V2O5 to produce
corrosion products (Fig. 15a). When the Y is exhausted, lattice vacancies
are formed simultaneously [29]. In the second step, the Y underneath
will occupy lattice vacancies due to the increasing mobility of Y by
NaVO3 and the high concentration of V [49]. The pores in coating A, B,
and C provide more paths for the leaching of Y, allowing it to choose the
closest path to be leached and react with V (Fig. 15b). Nevertheless, in
coating D, more flat regions allow Y can only be leached from the bottom
to the top and increase its barrier. The further down with a longer path,
the harder it is. Therefore, more YVO4 is found in pores, as shown in
Fig. 15(c). YVO4 precipitates a minimal soluble form with a high melting
point (1810 ºC) and continuously leaches the Y2O3 [42]. Although the
YVO4 has a blocking effect on the infiltration of V, lattice vacancies also
provide infiltration channels for V. Through these channels, V infiltrates
into the interior of the coating to generate corrosion products with Y,
Fig. 15. Schematic diagram showing the molten salt penetration of four YSZ coatings, (a) as-sprayed, (b) ground, (c) single-time LMGed, and (d) six-times LMGed.
11
Corrosion Science 209 (2022) 110731
inducing a phase transformation (t→‫׳‬m ZrO2) to form damage and
mineralization areas (Fig. 11). However, it is reported that since Y2O3
has an immobilizing effect on V, V will not infiltrate too deep, which
explains the reduced corrosion depth in coating A (Fig. 12) [50]. Fig. 16.
4. Conclusion
In this paper, the APS 8YSZ coatings were treated by a nanosecond
pulsed laser (laser micro glazing, LMG). The surface and cross-section
morphologies, phase composition, and hot corrosion behavior of 8YSZ
ceramic coatings were systematically investigated. The following con­
clusions can be drawn:
(1) A dense LMGed layer is well bonded with underlying splats after
the LMG process. Single-time LMG can only reduce the size of
pores, but six-times LMG can effectively eliminate surface pores.
(2) Extremely narrow microcracks (sub-micron level, <1 µm) are
prone to form in the LMGed layer. The surface roughness of the
six-times LMGed decreased from 6.704 µm to 2.890 µm, and the
phase composition is the same as the as-sprayed.
(3) The pores in the single-time LMGed layer seriously affect its hot
corrosion resistance. The concentration of V in them is high, and
the leaching distance of Y is shortened, which is beneficial for the
generation of corrosion products. The dense, non-pore LMGed
layer produced by six-times LMG can effectively prevent the
penetration of molten salts. The corrosion product YVO4 is sub­
stantially reduced and the depth of damaged area is diminished
from 37.073 µm to 20.918 µm.
(4) After six-times LMG process, the phase transformation was sup­
pressed during the hot corrosion tests. The volume fraction of m-
ZrO2 decreased from 53% to 27% and more block-shaped t′ -ZrO2
grains are densely packed together, which inhibits the penetra­
tion of molten salts.
CRediT authorship contribution statement
Kun Huo: Investigation, Data curation, Formal analysis, Writing –
original draft, Writing – review & editing. Fengze Dai: Conceptualiza­
tion, Resources, Funding acquisition, Supervision, Writing – review &
editing, Project administration. Wei Qian: Resources, Supervision,
Funding acquisition, Formal analysis. Yunxia Ye: Methodology, Inves­
tigation, Data curation. Jie Cai: Methodology, Investigation, Data
curation. Yinqun Hua: Methodology, Investigation, Data curation.
Xiaofeng Zhang: Methodology, Investigation, Data curation.
K. Huo et al.
Fig. 16. The schematic diagram of V diffusion and Y leaching.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
Data will be made available on request.
Acknowledgments
This work was supported by the Postgraduate Research & Practice
Innovation Program of Jiangsu Province (No. KYCX22_3619).
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